Processing of copper converter slag for metal reclamation. Part I: Extraction and recovery of copper and cobalt.

Clean processing of copper converter slag to reclaim cobalt and copper could be a challenge. An innovative and environmentally sound approach for recovering valuable metals from such a slag has been developed in the present study. Curing the slag with strong sulphuric acid, without re-smelting or roasting as practiced currently in the industry, render it accessible to leaching, and more than 95% of cobalt and up to 90% of copper was extracted together with iron by water leaching, leaving silica behind in a residue. The copper in the leach liquor was recovered by cementation with iron and the dissolved iron crystallized as ferrous sulphate monohydrate. The cobalt in the mother-liquor rich in iron was recovered by either cementation or sulphide precipitation. Operation variables in the new process were also investigated and optimized.     

Processing of copper converter slag for metals reclamation: Part II: mineralogical study.

Chemical and mineralogical characterizations of a copper converter slag, and its products obtained by curing with strong sulphuric acid and leaching with hot water, were carried out using ore microscopy, scanning electronic microscopy with energy dispersive spectrometry, wave-length dispersive X-ray fluorescence spectrometry, X-ray diffractometry and chemical phase analysis, which provided necessary information to develop a new process for treating such slag and further understanding of the chemical and mineralogical changes in the process.     

Recovery of copper and cobalt from ancient slag.

About 2.5 million tonnes of copper smelter slag are available in Küre, northern part of Turkey. This slag contains large amounts of metallic values such as copper and cobalt. A representative slag sample containing 0.98% Cu, 0.49% Co and 51.47% Fe was used in the experimental studies. Two different methods, direct acid leaching and acid baking followed by hot water leaching were used for recovering Cu and Co from the slag. The effects of leaching time, temperature and acid concentration on Cu- and Co-dissolving efficiencies were investigated in the direct acid leaching tests. The optimum leaching conditions were found to be a leaching time of 2 h, acid concentration of 120 g L(-1), and temperature of 60 degrees C. Under these conditions, 78% Cu and 90% Co were extracted. In the acid baking + hot water leaching tests, 74% Co was dissolved after 1 h of roasting at 200 degrees C using a 3:1 acid:slag ratio, whereas the Cu-dissolving efficiency was 79% and the total slag weight loss was approximately 50%.     

从废甲醇合成催化剂中回收铜锌

将废RK-05甲醇合成催化剂经过煅烧、浸取、精制等工序回收其中的铜和锌。经正交实验得到煅烧废催化剂的最优工艺参数为:废催化剂筛目100目,煅烧温度950℃,煅烧时间60 min。最佳浸取工艺条件为:废催化剂加入量约4 g/L,浸取温度75℃,浸取剂用量与理论用量体积比2.0~3.0,浸取剂浓度4.0 mol/L,浸取时间10min。精制工序制备CuO的最佳工艺条件为:锌粒与滤渣质量比为1.00,反应时间3 h,煅烧温度450℃,煅烧时间4 h。制备ZnO的最佳工艺条件为:煅烧温度800℃,煅烧时间60 min。回收的产品CuO纯度为99.1%,满足GB/T674—2003《化学试剂粉状氧化铜》中优级品的标准。回收的产品ZnO纯度为99.6%,满足GB/T3185—1992《氧化锌(间接法)》中一级品的标准。     

水淬铜渣技术要求标准研究

面对绿色发展的新形势,我国正在大力推进固废的资源化利用工作,提升标准化水平。论述了编制水淬铜渣标准的意义和作用,介绍了标准研制的原则,以及水淬铜渣的技术要求、试验方法、检验规则等,通过标准的研制与实施,将引领并规范水淬铜渣的应用。     

Production of brown and black pigments by using flotation waste from copper slag.

One of the major problems in copper-producing countries is the treatment of the large amount of copper slag or copper flotation waste generated from copper slag which contains significant amounts of heavy metals such as Cu, Zn, Pb and Co. Dumping or disposal of such large quantities of flotation waste from copper slag causes environmental and space problems. In this study, the treatment of flotation waste from copper slag by a thermal method and its use as an iron source in the production of inorganic brown and black pigments that are used in the ceramic industry were investigated. The pigments were produced by calcining different amounts of flotation waste and chromite, Cr2O3, ZnO and CoO mixtures. The pigments obtained were added to transparent ceramic glazes and porcelainized tile bodies. Their colours were defined by L*a*b* measurements with a spectrophotometer. The results showed that flotation waste from copper slag could be used as an iron source to produce brown and black pigments in both ceramic body and glazes.     

Study of the future land use of a contaminated site: Preferences versus potential use

Worldwide, agencies with high levels of contamination are faced with decisions about remediation and restoration. These decisions should be informed by future land use and long‐term stewardship goals. In the United States, the Department of Energy has lands in some 34 states that require cleanup. They are involved in massive remediation and restoration efforts on lands from the Cold War legacy and wish to reduce their overall footprint. Understanding future land use preferences is essential for determining the nature and degree of remediation and restoration. The objective of this study was to examine future land use preferences for the Department of Energy's Los Alamos National Laboratory as a function of ethnicity for attendees at the Los Alamos Gun Show in New Mexico (1999), and to determine whether their own activity influences future land use preferences. The highest preferred future land uses for Los Alamos National Laboratory were hiking, camping, National Environmental Research Park, and birdwatching, followed by hunting and fishing. Increased nuclear waste storage and building homes and factories were rated the lowest. Further, hiking and camping were rated higher than at two other DOE sites. There were few ethnic differences, although American Indians rated camping, hiking, building houses, and returning the land to American Indians higher than did others, and Hispanics rated using it for a preserve as a higher preferred land use than all others. The differences, however, were not great. Relative ratings for using the land for hunting and fishing were directly related to individual frequency of hunting and fishing for both whites and Hispanics, indicating that people perceive the importance of land use by how they want to use it. Ratings for hiking and camping were not related to the number of days people hiked and camped, suggesting these are general preferences overall. © 2004 Wiley Periodicals, Inc.     

铜渣催化H2O2氧化处理棉浆黑液

采用铜渣催化H2O2类Fenton氧化反应处理棉浆黑液,研究了酸析pH、H2O2投加量、铜渣投加量对棉浆黑液COD和TOC去除率及溶出Fe2+质量浓度的影响,考察了铜渣重复使用性能,讨论了铜渣催化作用机制.结果表明:在酸析pH为2、H2O2投加量为25 mmol/L、铜渣投加量为2.5 g/L条件下,反应180 min...     

Kinetics and thermodynamics of copper ions removal from wastewater by use of zeolite.

Natural Bulgarian zeolite was tested for its ability to remove Cu2+ from model wastewater. Influence of process variables was investigated. It was found that the optimum wastewater to zeolite ratio is 100:1 and the optimum pH value of water to be treated is 5.5 to 7.5. Zeolite with finer particles shows a higher uptake capacity. The simultaneous presence of Ca2+ and Mg2+ in concentrations similar to their concentrations in Bulgarian natural water does not significantly influence the uptake of Cu2+. Zeolite modification by treating it with NaCl, CH3COONa and NaOH increases its uptake ability. Copper ions are strongly immobilized by modified zeolite and secondary pollution of water caused by its contact with preloaded zeolite is very low (1.5-2.5% of Cu2+ preliminary immobilized have been released back into acidified water). Contacting with 2 mol dm(-3) NaCl can easily regenerate loaded zeolite; best results were obtained for zeolite modified with NaCl. Requirements of Bulgarian standards for industrial wastewater can be met by a one-stage process for an initial Cu2+ concentration of 10 mg dm(-3), and by a two stage process for an initial Cu2+ concentration of 50 mg dm(-3). Uptake of Cu2+ by zeolite from neutral wastewater has proved to be as effective as Cu2+ removal by precipitation of copper hydroxide. The process of Cu2+ uptake by natural zeolite is best described by the kinetic equation for adsorption. This fact, together with the correlation found between the Cu2+ uptake and the amount of Na+, Ca2+ and K+ released into solution by zeolite shows that the ion exchange sorption plays the basic role in Cu2+ uptake by natural zeolite. The value obtained for the apparent activation energy (26.112 kJ mol(-1) implies that the process can be easily carried out with a satisfactory rate. The uptake equilibrium is best described by the Langmuir adsorption isotherm, with Langmuir constants KL= 6.4 x 10(-2) dm3 mg(-1) and M = 6.74 mg g(-1). The apparent equilibrium constant found shows moderate affinity of zeolite for Cu2+. Values of deltaG degrees and deltaH degrees found show the spontaneous and endothermic nature of the process of Cu2+ uptake by natural zeolite.     

Use of slag for dye removal

Adsorption techniques employing activated carbon have been found to be reasonably effective in the removal of some of the ionic impurities in water. However, economic considerations may require the use of inexpensive sorbents which are either naturally available or available as waste products from manufacturing processes. Slag is one such waste product obtained during the manufacture of steel, and the present study investigates dye removal characteristics of slag from colored waters. Aqueous solutions prepared from commercial grade acid, basic, and disperse dyes were used in this study, and batch pH, kinetic, and isotherm studies were undertaken on a laboratory scale. The data were evaluated for applicability to the Langmuir, Freundlich, and BET isotherm models, and the removal capacity of slag was compared with that of granular activated carbon. Results indicated approximately 94% removal of the disperse dye by slag, compared with a removal of approximately 49% achieved by activated carbon. Removal of acid dyes (dyes containing anionic groups) was reasonably good (approximately 47 and 74%), though not as good as obtained using activated carbon (approximately 100%). Column studies were conducted with a disperse dye (nonionic, slightly soluble in water), and analysis of data showed a sorption capacity of 1.3 mg of disperse dye per gram of slag. However, effluent dye concentrations were found to be higher than the permissible levels for discharge to receiving waters.     

Impact of land use on soluble organic nitrogen in soil

Although it has been hypothesized that soluble organic nitrogen (SON) plays a central role in regulating productivity in some terrestrial ecosystems, the factors controlling the size of the SON pool in soil remain poorly understood. Therefore our principal aim in this work was to assess the impact of seven different land use systems (rough and managed grassland, deciduous and coniferous woodland, heathland, wetland and tilled land) on the size of the SON and inorganic N (NO^? ₃, NH⁺ ₄) pools in the surface soil layer (0–15 cm). After extraction with deionised water, we found that in most cases the size of the water extractable organic N (WEON) pool was similar in size to the inorganic N pool. In contrast, the KCl extractable organic N (KClEON) pool constituted the dominant form of soluble N in soils under all land uses, perhaps indicating that significant amounts were held on the soil exchange phase. In contrast to inorganic N, which varied significantly with land use, the size of the KClEON and WEON pool was similar for all land uses with the exception of KClEON in tilled land, where significantly lower amounts were observed. We conclude that SON constitutes an important soil N pool in a broad range of land uses, and that its role in microbial N assimilation, plant nutrition and ecosystem responses to atmospheric N deposition warrants further attention.     

Application of magnetic separation to steelmaking slags for reclamation

Integrated iron and steel plants generate large amounts of metallurgical slag, which usually contains some quantity of metals or mixtures of oxides that could be treated to be recycled in various applications. The conventional method for disposal of slags is dumping. However, it is possible to process the slags to be used in the production of metallic iron, or as an additive in cement making. In this study, a basic oxygen furnace (BOF) steelwork slag obtained from the Kardemir integrated iron and steel works, Karabuk, Turkey is used. A drum magnetic separator system with pre-engineered crucial processing parameters of drum revolution speed, drum radius, drum flesh thickness, and magnitude of the magnetic field applied is utilized, as these parameters have a competing influence on the results. Subsequently, the effects of slag grain size and the drum-blade gap are investigated in the separation efficiency of magnetic grains. It is found that collection of magnetic grains is improved by decreasing the grain size of slags and moreover, the collection of magnetic grains fraction is increased with an increase in the gap between the blades and drum.     

Reprocessing of metallurgical slag into materials for the building industry

Several methods of reprocessing metallurgical (blast furnace) slag into materials for the building industry, based on melting aggregates with submerged combustion, were developed and tested. The first method involves melting hot slag with some additives directly in a slag ladle with a submerged gas-air burner, with the objective of producing stabilized slag or glass-ceramic. The second method involves direct draining of melted slag from a ladle into the slag receiver, with subsequent control of the slag draining into the converter where special charging materials are added to the melt, with the objective of producing glass-ceramic. A third method involves melting cold slag with some additives inside a melting converter with submerged gas-air burners, with the objective of producing glass-ceramic fillers for use in road construction. Specific to the melting process is the use of a gas-air mixture with direct combustion inside the melt. This feature provides melt bubbling to help achieve maximum heat transfer from combustion products to the melt, improve mixing (and therefore homogeneity of the melt), and increases the rate of chemical reactions. The experimental data for different aspects of the proposed methods are presented. The reprocessed blast-furnace slag in the form of granules can be used as fillers for concretes, asphalts, and as additives in the production of cement, bricks and other building materials. As well, reprocessed blast-furnace slag can be poured into forms for the production of glass-ceramic tiles.     

Assessment of the methane oxidation capacity of compacted soils intended for use as landfill cover materials

The microbial oxidation of methane in engineered cover soils is considered a potent option for the mitigation of emissions from old landfills or sites containing wastes of low methane generation rates. A laboratory column study was conducted in order to derive design criteria that enable construction of an effective methane oxidising cover from the range of soils that are available to the landfill operator. Therefore, the methane oxidation capacity of different soils was assessed under simulated landfill conditions. Five sandy potential landfill top cover materials with varying contents of silt and clay were investigated with respect to methane oxidation and corresponding soil gas composition over a period of four months. The soils were compacted to 95% of their specific proctor density, resulting in bulk densities of 1.4-1.7 g cm⁻³, reflecting considerably unfavourable conditions for methane oxidation due to reduced air-filled porosity. The soil water content was adjusted to field capacity, resulting in water contents ranging from 16.2 to 48.5 vol.%. The investigated inlet fluxes ranged from 25 to about 100 g CH₄ m⁻² d⁻¹, covering the methane load proposed to allow for complete oxidation in landfill covers under Western European climate conditions and hence being suggested as a criterion for release from aftercare. The vertical distribution of gas concentrations, methane flux balances as well as stable carbon isotope studies allowed for clear process identifications. Higher inlet fluxes led to a reduction of the aerated zone, an increase in the absolute methane oxidation rate and a decline of the relative proportion of oxidized methane. For each material, a specific maximum oxidation rate was determined, which varied between 20 and 95 g CH₄ m⁻² d⁻¹ and which was positively correlated to the air-filled porosity of the soil. Methane oxidation efficiencies and gas profile data imply a strong link between oxidation capacity and diffusive ingress of atmospheric air. For one material with elevated levels of fine particles and high organic matter content, methane production impeded the quantification of methane oxidation potentials. Regarding the design of landfill cover layers it was concluded that the magnitude of the expected methane load, the texture and expected compaction of the cover material are key variables that need to be known. Based on these, a column study can serve as an appropriate testing system to determine the methane oxidation capacity of a soil intended as landfill cover material.     

酸性氯化铜蚀刻废液一步沉淀法制备碱式碳酸铜

以酸性氯化铜蚀刻废液为原料,在Na₂CO₃和助剂A存在下,采用一步沉淀法制备碱式碳酸铜。考察了反应pH、n（Na₂CO₃）∶n（助剂A）、反应时间和反应温度对碱式碳酸铜制备效果的影响,并采用XRD、TG 及SEM对产品进行了表征。实验结果表明：在反应pH 7.0、沉淀剂配比n（Na₂CO₃）∶n（助剂A）=1∶2、反应时间1.0 h、反应温度70 ℃的条件下,产品的w（Cu²⁺）达55.62%,w（Cl^-）为0.013%,符合HG/T 4825—2015《工业碱式碳酸铜》的要求;蚀刻废液中Cu²⁺的回收率接近100%。表征结果表明,制得的产品为单一组分CuCO₃·Cu（OH）₂,小颗粒为直径1.8~5.4 μm的不规则球形,团聚后的大颗粒呈姜块状形貌,粒径为48~75 μm。     

Institutional controls for future land use at active installation restoration program (IRP) sites

One of the strategies now in vogue in hazardous waste cleanup is basing remedial strategies on future land use. The initial thrust of CERCLA for permanent and complete remedies has given way, pushed by concepts like “brownfields” and base closure and reuse, to strategies often based on “institutional controls” that attempt to stabilize future land uses at a site based on residual risk. The heart of this concept is that instead of removing all wastes from a site, some wastes can safely remain so long as in the future the site is not used in such a way that the residual contamination poses an unacceptable risk to human health and the environment. “Institutional controls” is a term for land use management strategies that do not rely on engineering approaches to reduce risk, but rather seek to ensure that the site is not used in an inappropriate way in the future. This article cautions that such a strategy has inherent residual risks that must be understood by those involved in implementing hazardous waste cleanups and those responsible for future uses of contaminated property. Simply put, institutional controls are only as good as the processes that are in place to ensure they are respected in the future. This presents particular problems for active duty installations because most of the protections commonly available to private sector sites are not useful at active installations. This article discusses an initiative by the Air Combat Command to develop a handbook on instituting and maintaining land restrictions. It will also discuss that effort in light of the April 21 EPA Region IV guidance on assuring Land Use Controls at Federal Facilities. This article is based on a paper and presentations given at the 1998 ACC Environmental Training Symposium.     

The use of waste basic oxygen furnace slag and hydrogen peroxide to degrade 4-chlorophenol

A new treatment method is developed to degrade 4-chlorophenol (4-cp) and its oxidation intermediates. The experimental results of this research demonstrate that 4-cp and its oxidation intermediates can be decomposed completely by basic oxygen furnace slag (BOF slag) with hydrogen peroxide (H₂O₂) in an acid solution. The factors that effect the treatment efficiency were studied including initial concentration of 4-cp, pH of the solution, concentration of H₂O₂ and amount of BOF slag. The BOF slags are final waste materials in the steel making process. The major components of BOF slag are CaO, SiO₂, Fe₂O₃, FeO, MgO and MnO. As the BOF slag in an acid solution, FeO and Fe₂O₃ can be dissociated to produce ferrous ion and ferric ion. Ferrous ion reacts with hydrogen peroxide to form “Fenton's reagent” which can produce hydroxyl radicals (OH^.). Hydroxyl radical possession of high oxidation ability can oxidize organic chemicals effectively. Results show that 100 mg/l of 4-cp is decomposed completely within 30 min by 438.7 g/l BOF slag with 8.2 mM hydrogen peroxide in pH=2.8±0.2 solution. The COD value of the solution is reduced from 290 to 90 mg/l. The factors studied which affect the 4-cp decomposition efficiency were the hydrogen peroxide concentration, BOF slag concentration, pH of the solution and initial concentration of 4-cp. Because large amounts of Fe₂O₃ and FeO are present in the BOF slag, the BOF slag not only has a high treatment efficiency, but also can be used repeatedly.     

Review on the innovative uses of steel slag for waste minimization

Piles of steel slag, a solid waste generated from the iron and steel industry, could be seen due to no utility found for the past century. Steel slag has now gained much attention because of its new applications. The properties of slag greatly influence its use and thus had got varied applications. The chemical composition of steel slag varies as the mineral composition of raw material such as iron ore and limestone varies. This paper reviews the characteristics of steel slag and its usage. The paper reviews recent developments in well-known applications to the steel slag such as aggregate in bituminous mixes, cement ingredient, concrete aggregate, antiskid aggregate, and rail road ballast. This paper also reviews novel uses such as mechanomutable asphalt binders, building material, green artificial reefs, thermal insulator, catalyst and ceramic Ingredient. The review is also done on utilization of solid waste for waste management by the novel methods like landfill daily cover material, sand capping, carbon sequestration, water treatment and solid waste management. Review also shows recovery of pure calcium carbonate and heavy metals from slag, providing opportunity for revenue generation. Steel slag once traded as free to use by steel industries is now sold in the market at some price. Its utilization is of great economic significance as it also contributes to the reduction of solid waste.